EP2231572A1 - Production of propylene glycol monoalkyl ether - Google Patents
Production of propylene glycol monoalkyl etherInfo
- Publication number
- EP2231572A1 EP2231572A1 EP08870913A EP08870913A EP2231572A1 EP 2231572 A1 EP2231572 A1 EP 2231572A1 EP 08870913 A EP08870913 A EP 08870913A EP 08870913 A EP08870913 A EP 08870913A EP 2231572 A1 EP2231572 A1 EP 2231572A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- propylene glycol
- glycol monoalkyl
- monoalkyl ether
- alkali metal
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 102
- -1 propylene glycol monoalkyl ether Chemical class 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000004821 distillation Methods 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 30
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 18
- 238000002835 absorbance Methods 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 21
- 239000012279 sodium borohydride Substances 0.000 claims description 14
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 13
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims 1
- MKNZKCSKEUHUPM-UHFFFAOYSA-N potassium;butan-1-ol Chemical compound [K+].CCCCO MKNZKCSKEUHUPM-UHFFFAOYSA-N 0.000 claims 1
- AWDMDDKZURRKFG-UHFFFAOYSA-N potassium;propan-1-olate Chemical compound [K+].CCC[O-] AWDMDDKZURRKFG-UHFFFAOYSA-N 0.000 claims 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 claims 1
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 15
- 239000012535 impurity Substances 0.000 abstract description 11
- 239000000047 product Substances 0.000 description 16
- 239000011541 reaction mixture Substances 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 229940044613 1-propanol Drugs 0.000 description 5
- 229960004592 isopropanol Drugs 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 238000000998 batch distillation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001944 continuous distillation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 2
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 2
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 2
- QTDSKVOHJOFQES-UHFFFAOYSA-N 1-methoxybut-3-en-2-one Chemical compound COCC(=O)C=C QTDSKVOHJOFQES-UHFFFAOYSA-N 0.000 description 1
- CUZLJOLBIRPEFB-UHFFFAOYSA-N 1-methoxypropan-2-one Chemical compound COCC(C)=O CUZLJOLBIRPEFB-UHFFFAOYSA-N 0.000 description 1
- GQCZPFJGIXHZMB-UHFFFAOYSA-N 1-tert-Butoxy-2-propanol Chemical compound CC(O)COC(C)(C)C GQCZPFJGIXHZMB-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/44—Separation; Purification; Stabilisation; Use of additives by treatments giving rise to a chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
Definitions
- This invention relates to a process for producing a propylene glycol monoalkyl ether.
- Propylene glycol monoalkyl ethers are high-performance industrial solvents for paints and coatings, cleaners, inks, and a variety of other applications, including agricultural, cosmetic, electronic, textile, and adhesive products. They are also used as chemical intermediates for end-products such as propylene glycol ether acetates.
- propylene glycol monoalkyl ethers are formed by the reaction of propylene oxide with an alcohol, such as methanol or 1-butanol.
- an alcohol such as methanol or 1-butanol.
- a catalyst is not required, the reaction is typically performed in the presence of a catalyst.
- the catalysts used in this process include acidic, basic, and neutral species.
- Particularly useful catalysts include acids such as sulfuric acid, boric acid and some fluorine-containing acids; or bases such as alkali and alkaline earth metal hydroxides and alkoxides, tertiary amines, and certain metal oxides.
- acids such as sulfuric acid, boric acid and some fluorine-containing acids
- bases such as alkali and alkaline earth metal hydroxides and alkoxides, tertiary amines, and certain metal oxides.
- G. B. Pat. No. 271 ,169 discloses the use of sulfuric acid, alkali metal alkoxides, and alkali metal salts of lower fatty acids.
- U.S. Pat. No. 2,327,053 teaches the use of metal halides such as stannic halides, antimony pentahalides, aluminum halides, zinc halides and ferric halides.
- carbonyl impurities such as formaldehyde, acetaldehyde, propionaldehyde, acetone, methoxy acetone, and methoxy butenone
- new processes to produce propylene glycol monoalkyl ethers are needed.
- the invention is a process which comprises: (a) reacting propylene oxide and an alcohol in the presence of an alkali or alkaline earth metal alkoxide catalyst to produce an alkoxylation mixture comprising propylene glycol monoalkyl ether; (b) distilling the alkoxylation mixture to produce a first overhead stream comprising propylene oxide and the alcohol and a first bottoms stream comprising propylene glycol monoalkyl ether; and (c) distilling the first bottoms stream to produce purified propylene glycol monoalkyl ether as a second overhead stream, wherein the reaction and/or one or more of the distillation steps occur in the presence of alkali metal borohydride.
- the process surprisingly reduces the carbonyl impurity level and UV absorbance in the propylene glycol monoalkyl ether.
- the process of the invention comprises first reacting a reaction mixture comprising propylene oxide and an alcohol in the presence of an alkali or alkaline earth metal alkoxide to produce an alkoxylation mixture comprising a propylene glycol monoalkyl ether.
- a reaction mixture comprising propylene oxide and an alcohol
- an alkali or alkaline earth metal alkoxide to produce an alkoxylation mixture comprising a propylene glycol monoalkyl ether.
- two propylene glycol monoalkyl ether isomers 1-alkoxy-2-propanol and 2-alkoxy-1-propanol
- the reaction of propylene oxide and methanol produces both 1-methoxy-2-propanol (known as "PM-1") and 2-methoxy-1-propanol ("PM-
- PM-1 the major product from methanol propoxylation, is the isomer sold commercially.
- propylene glycol monoalkyl ethers are commercially available products.
- Commercial products include Lyondell Chemical Company's ARCOSOLV® propylene glycol ethers, such as ARCOSOLV PM (propylene glycol monomethyl ether), ARCOSOLV PNB (propylene glycol normal butyl ether), ARCOSOLV PTB (propylene glycol tertiary butyl ether), and ARCOSOLV PNP (propylene glycol normal propyl ether).
- the reaction mixture comprises propylene oxide and an alcohol.
- the alcohol used for the reaction is suitably an aliphatic, cycloaliphatic or an aromatic alcohol and may have one, two, or more hydroxyl groups. Preferably, the alcohol has only one hydroxyl group.
- the alcohol may be primary, secondary or tertiary in structure, and may be saturated or unsaturated as well as substituted with various substituents. Most preferably, the alcohol is a CrC 4 alcohol, particularly, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and tert-butanol.
- the relative amounts of propylene oxide and alcohol that make up the reaction mixture can vary over a fairly wide range. Usually, however, it is preferred to use at least one mole of alcohol for every propylene oxide equivalent. For example, when methanol reacts with propylene oxide to produce propylene glycol monomethyl ether, it is preferred to use about 2 moles of methanol per mole of propylene oxide.
- the molar ratio of alcohol to propylene oxide is at least 1.1 :1 and is more preferably in the range from 1.5:1 to 5:1.
- the reaction mixture may also include a solvent.
- Suitable solvents include C 5 -C 2O aliphatic hydrocarbons such as hexane, C6-C 20 aromatic hydrocarbons such as toluene, nitriles such as acetonitrile, and ethers such as methyl t-butyl ether.
- the reaction of propylene oxide with an alcohol is performed in the presence of an alkali or alkaline earth metal alkoxide catalyst.
- an alkali or alkaline earth metal alkoxide catalyst any alkali or alkaline earth metal alkoxide may be used (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, or barium alkoxides), alkali metal alkoxides are preferred. Potassium alkoxides and sodium alkoxides are particularly preferred.
- Preferred sodium alkoxides include sodium methoxide, ethoxide, n-propoxide, and n-butoxide, and t-butoxide.
- Preferred potassium alkoxides include potassium methoxide, ethoxide, n-propoxide, n-butoxide, and t-butoxide.
- the alkoxide corresponds to the alcohol used in the reaction, that is, if the alcohol is methanol then the alkoxide is a methoxide such as sodium methoxide or potassium methoxide.
- the reaction of propylene oxide and alcohol to form propylene glycol monoalkyl ether is preferably carried out at a temperature in the range of from about 50 0 C to about 25O 0 C, more preferably from about 100 0 C to about 180 0 C.
- the reaction between propylene oxide and the alcohol is exothermic, so it may be desirable to apply cooling to the reaction mixture in order to control the reaction temperature.
- the reaction is preferably carried out at atmospheric pressure or at higher pressure up to about 3000 psig (20,786 MPa).
- the reaction step of the invention includes batch, semi-batch, and continuous processes.
- the reactants except for the catalyst
- catalyst is introduced, and the mixture is heated to the desired reaction temperature to form an alkoxylation mixture comprising propylene glycol monoalkyl ether.
- streams of the propylene oxide, alcohol, any recycle streams, and alkali or alkaline earth metal alkoxide catalyst are fed continuously into a heated reaction zone to form an alkoxylation mixture comprising propylene glycol monoalkyl ether which is continuously withdrawn from the reactor.
- the alkoxylation mixture is subjected to distillation in order to produce a propylene glycol monoalkyl ether product.
- the distillation steps include first distilling the alkoxylation mixture to produce a first overhead stream comprising propylene oxide and alcohol and a first bottoms stream comprising propylene glycol monoalkyl ether; and then distilling the first bottoms stream to produce purified propylene glycol monoalkyl ether as a second overhead stream.
- the first distillation step distilling the alkoxylation mixture
- the alkoxylation mixture Prior to distillation, the alkoxylation mixture may be sent to a storage unit and/or a finishing drum in order to remove lights from the alkoxylation mixture, however such a storage unit or finishing drum is not necessary for the process of the invention. If the alkoxylation mixture is sent to a finishing drum, the system pressure in the finishing drum is reduced such that a significant amount of unreacted propylene oxide is flashed and vented from the alkoxylation mixture prior to distillation. This flashed propylene oxide may be recycled back to the reaction.
- the second distillation step distilling the first bottoms stream, may be operated at any temperature and pressure which will afford purified propylene glycol monoalkyl ether as the second overhead stream.
- the purified propylene glycol monoalkyl ether may be a mixture of 1-alkoxy-2-propanol and 2-alkoxy-1- propanol.
- the purified propylene glycol monoalkyl ether may also be purified 1- alkoxy-2-propanol, wherein any 2-alkoxy-1-propanol produced is separated in the second bottoms stream.
- the distillation towers (also referred to as columns) may be of conventional design. The towers are preferentially packed with conventional packing. The temperature and pressure in the towers may be adjusted depending on the type of propylene glycol monoalkyl ether produced.
- the first distillation tower is used in order to remove alcohol and propylene oxide as an overhead stream and concentrate propylene glycol monoalkyl ether in the bottoms stream.
- the first distillation tower is operated at a temperature of from about 50 0 C to about 200 0 C and a pressure of from about 1 psig (108 MPa) to about 150 psig (1136 MPa).
- the overhead from the first distillation tower (containing unreacted alcohol and propylene oxide) is preferentially recycled to the reaction step for further reaction.
- the first distillation bottoms comprising propylene glycol monoalkyl ether, exits the first tower and is transferred to the second distillation tower for further purification of the propylene glycol monoalkyl ether.
- the first distillation bottoms stream is distilled.
- the overhead stream from the second distillation tower comprises high purity propylene glycol monoalkyl ether.
- the second distillation bottoms stream comprising heavier byproducts (such as dipropylene glycol ethers and tripropylene glycol ethers), and optionally 2-alkoxy-1-propanol where 1-alkoxy-2- propanol is purified in the overhead stream, may be recycled back to the reactor or purified further to produce other products.
- the second distillation tower is operated at a temperature of from about 100° to about 200 0 C and a pressure of from about 1 mm Hg (0.133 MPa) to about 760 mm Hg (101.3 MPa).
- the purity of the propylene glycol monoalkyl ether stream exiting as an overhead stream from the second distillation column is usually in the range from about 99 to about 99.95 percent.
- the propylene glycol monoalkyl ether product typically contains by weight greater than 50 ppm of various carbonyl impurities and gives a UV absorbance (at 245 nm) of greater than 1.
- the propylene glycol monoalkyl ether produced with no alkali metal borohydride comprises by weight about 50 to 2,000 ppm of various carbonyl impurities, usually about 50 to 1 ,000 ppm.
- the process of the invention requires that the reaction and/or one or more of the distillation steps occur in the presence of an alkali metal borohydride.
- alkali metal borohydride surprisingly reduces the carbonyl concentration and UV absorption in the propylene glycol monoalkyl ether product.
- any alkali metal borohydride may be used (lithium, sodium, potassium, rubidium, and cesium borohydride), sodium and lithium borohydride are preferred, and sodium borohydride is especially preferred.
- the alkali metal borohydride is preferably added to the reaction mixture such that the reaction mixture comprises from about 0.05 to 100 ppm alkali metal borohydride, more preferably from about 0.1 to 50 ppm alkali metal borohydride.
- the alkali metal borohydride may be added into the distillation column as a separate stream from the alkoxylation mixture or may be added into the alkoxylation mixture prior to the first distillation step.
- the alkali metal borohydride is added into the alkoxylation mixture prior to the first distillation step.
- the alkali metal borohydride is preferably added to the alkoxylation mixture such that the alkoxylation mixture comprises from about 0.1 to 1 ,000 ppm alkali metal borohydride, more preferably from about 1 to 100 ppm alkali metal borohydride.
- the alkali metal borohydride may be added into the distillation column as a separate stream from the first bottoms stream or may be added into the first bottoms stream prior to the second distillation step.
- the alkali metal borohydride is added into the first bottoms stream prior to the second distillation step.
- the alkali metal borohydride is preferably added to the first bottoms stream such that the first bottoms stream comprises from about 1 to 10,000 ppm alkali metal borohydride, more preferably from about 1 to 100 ppm alkali metal borohydride.
- alkali metal borohydride may be added to the reaction step and both distillation steps, it is preferable to add alkali metal borohydride to the first and/or the second distillation step. It is especially preferred to add the alkali metal borohydride to the first distillation step.
- a purified propylene glycol monoalkyl ether product having a decreased carbonyl impurities content is produced.
- the purified propylene glycol monoalkyl ether product has a UV absorbance, at 245 nm, of 1 or less.
- Comparison Run 1A Methanol (132 g), propylene oxide (110 g), and a 2- methoxy-1-propanol recycle mixture (60 g) are added to a stainless steel reactor and the temperature of the reaction mixture is raised to 13O 0 C.
- a potassium methoxide catalyst mixture (1.27 g, of 25 wt.% KOCH 3 in methanol) is added to the reaction mixture and stirred. Samples are taken from the reaction mixture periodically (at 1 h and 10 min and at 2 hr and 10 min after catalyst addition) and analyzed for carbonyl content and UV absorbance. Results are shown in Table
- Run 1 B Run 1 B is run according to the procedure of Comparison Run 1A with the exception that NaBH 4 is added to the reaction mixture with the methanol, resulting in a 0.3 ppm NaBH 4 concentration in the reaction mixture. Results are shown in Table 1.
- Comparison Run 2A A 1 -methoxy-2-propanol reaction solution (1 198.3 g, containing 778.19 g PM-1 ) is distilled under vacuum using an 8 mm I. D. spinning band batch distillation column (B/R Instrument Corporation, Easton MD). The condenser pressure is controlled at 368 mm Hg (49 MPa) and the reflux ratio is set at 50 to 1. This results in a boiling temperature of 105 0 C in the distillation reboiler pot. Samples of the overhead, purified PM-1 are taken in 20 mL increments and analyzed for carbonyl content and UV absorbance (at 245 nm). Results are shown in Table 2.
- Run 2B Run 2B is run according to the procedure of Comparison Run 2A with the exception that 200 ppm NaBH 4 (0.24 g) is added to the 1 -methoxy-2- propanol solution (1200 g, containing 779.29 g PM-1 ). Results are shown in Table 2.
- Comparison Run 3A A 1 -methoxy-2-propanol reaction solution, containing 65 wt.% PM-1 , is purified by continuous distillation under vacuum using a distillation column (1 in. I. D. x 4 ft) containing PRO-PAK® packing.
- the 1 -methoxy-2-propanol reaction solution is fed into the distillation column at 18 inches from the bottom of the column and the temperature at the feeding tray is maintained at 1 18-1 19°C during the distillation procedure. Feed rate is adjusted to reach a desired liquid residence time.
- the reboiler liquid volume is controlled at 220 mL and pot temperature is maintained at 121-122°C.
- the reflux ratio is controlled at 5 to 1.
- Purified PM-1 product is withdrawn continuously overhead. PM-1 product samples are analyzed for carbonyl content and UV absorbance (at 245 nm). Results are shown in Table 3.
- Run 3B Run 3B is run according to the procedure of Comparison Run 3A with the exception that 42 ppm NaBH 4 is added to the 1 -methoxy-2-propanol reaction solution. Results are shown in Table 3. The results show that the addition of sodium borohydride into the continuous distillation reduces both carbonyl impurities and UV absorbance for the PM-1 product collected overhead.
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US12/009,212 US9187392B2 (en) | 2008-01-17 | 2008-01-17 | Production of propylene glycol monoalkyl ether |
PCT/US2008/012827 WO2009091379A1 (en) | 2008-01-17 | 2008-11-14 | Production of propylene glycol monoalkyl ether |
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EP2231572B1 EP2231572B1 (en) | 2012-06-27 |
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US (1) | US9187392B2 (en) |
EP (1) | EP2231572B1 (en) |
JP (1) | JP5837749B2 (en) |
KR (2) | KR101896755B1 (en) |
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WO2013112395A1 (en) * | 2012-01-27 | 2013-08-01 | Dow Global Technologies Llc | Method for reducing color in used lubricating oil |
US20150094463A1 (en) | 2012-03-30 | 2015-04-02 | Ube Industries, Ltd. | Hydroxyalkylated polyrotaxane production method |
PL2848602T3 (en) * | 2012-05-11 | 2021-05-31 | Sumitomo Chemical Company Limited | Method for producing glycols from oxirane compound |
CN102964222A (en) * | 2012-11-13 | 2013-03-13 | 宁波杭州湾新区珠峰企业管理服务有限公司 | Method for synthesizing propylene glycol ether |
WO2016017387A1 (en) * | 2014-07-30 | 2016-02-04 | 昭和電工株式会社 | Method for separating and recovering alkylene glycol monoalkyl ether, method for recycling liquid waste from processing of resist composition, and method for recycling resist composition processing liquid |
CN104230678B (en) * | 2014-09-10 | 2016-01-20 | 百川化工(如皋)有限公司 | A kind of method of producing dipropylene and tripropylene glycol butyl ether |
KR101939957B1 (en) * | 2015-10-12 | 2019-01-17 | 라이온델 케미칼 테크놀로지, 엘.피. | Preparation of propylene glycol monoalkyl ether |
CN107162882B (en) * | 2017-07-04 | 2020-10-02 | 中国科学院过程工程研究所 | Spray tower tray type reactor, system and process for producing propylene glycol monomethyl ether by using same |
WO2021172898A1 (en) * | 2020-02-26 | 2021-09-02 | 영남대학교 산학협력단 | Apparatus and method for manufacturing propylene glycol methyl ether acetate |
CN111454128B (en) * | 2020-04-22 | 2022-08-05 | 上海多纶化工有限公司 | Production method of fatty alcohol-polyoxyethylene ether |
JP6916402B1 (en) * | 2021-02-01 | 2021-08-11 | 株式会社日本触媒 | Method for producing secondary alcohol alkoxylate |
KR102399263B1 (en) * | 2021-08-09 | 2022-05-17 | 에스케이머티리얼즈퍼포먼스 주식회사 | Process for the preparation of propylene glycol monomethyl ether acetate |
KR102498772B1 (en) * | 2021-11-29 | 2023-02-10 | 주식회사 켐트로닉스 | Manufacturing method of ultra-high purity PGMEA |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB271169A (en) | 1900-01-01 | |||
US2035383A (en) * | 1933-03-18 | 1936-03-24 | Carbide & Carbon Chem Corp | Preservation of organic solvents |
US2327053A (en) | 1939-11-18 | 1943-08-17 | Shell Dev | Production of hydroxy ethers |
US3146272A (en) * | 1959-04-02 | 1964-08-25 | Dow Chemical Co | Antioxidants for glycol derivatives |
US3168569A (en) * | 1960-02-01 | 1965-02-02 | Mo Och Domsjoe Ab | Method of bleaching polyalkylene ethers |
US3205269A (en) * | 1960-05-10 | 1965-09-07 | Union Carbide Corp | Stabilization of ethers with phosphorous compounds |
US3347934A (en) * | 1966-02-28 | 1967-10-17 | Rohm & Haas | Process for the preparation of alkoxymethoxyalkanols |
US3374275A (en) * | 1966-05-24 | 1968-03-19 | Union Carbide Corp | Stabilization of polyoxyalkylene compounds |
US3972948A (en) * | 1974-11-29 | 1976-08-03 | Jefferson Chemical Company, Inc. | Anhydrous catalyst for manufacture of glycol ethers |
JPS5615229A (en) | 1979-07-17 | 1981-02-14 | Daicel Chem Ind Ltd | Production of alkoxypropanol |
CA1195696A (en) | 1982-04-09 | 1985-10-22 | Eugene G. Harris | Process for the production of ethylene glycol monoaryl ethers |
JPS61186337A (en) | 1985-02-13 | 1986-08-20 | Nippon Shokubai Kagaku Kogyo Co Ltd | Stabilized secondary alcohol ethoxylate |
JPS61246140A (en) | 1985-04-23 | 1986-11-01 | Nippon Shokubai Kagaku Kogyo Co Ltd | Stabilized alkylene oxide adduct to polyhydric alcohol |
JPH05246920A (en) | 1992-03-02 | 1993-09-24 | Kao Corp | Glycol ether having good smell and its production |
JPH05294880A (en) | 1992-04-16 | 1993-11-09 | Kao Corp | Production of alkylene oxide adducts to polyhydric alcohols |
DE19757709A1 (en) * | 1997-12-23 | 1999-07-01 | Basf Ag | Process for the preparation of oxyalkylated amines |
US7182841B2 (en) | 2003-04-23 | 2007-02-27 | Huntsman International Llc | Purification of solvents used for the purification of alkylene oxide |
CN1597649A (en) | 2004-08-04 | 2005-03-23 | 河北工业大学 | Method of synthesizing 2-hydroxyproply method ether using loading type aldaline catalyst |
CN1699320A (en) | 2005-04-22 | 2005-11-23 | 江苏华伦化工有限公司 | Production process for preparing propylene glycol ether |
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US20090187049A1 (en) | 2009-07-23 |
JP2011509998A (en) | 2011-03-31 |
CN101918347A (en) | 2010-12-15 |
US9187392B2 (en) | 2015-11-17 |
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